JPS61176639A - Production of sheet material - Google Patents

Abstract

PURPOSE:To obtain a sheet material having improved wet film-forming properties and hydrolysis resistance, and improved surface appearance with day, by adding a specific polyoxyalkylene modified polysiloxane compound to a polyurethane solution, applying the solution to a substrate, and subjecting it to wet treatment. CONSTITUTION:A polyoxyalkylene modified polysiloxane shown by 5-30wt% polyurethane solution (preferably solution in dimethylformamide, etc.) is blended with <=10wt%, preferably 0.5-5wt% based on solid content of a polyoxyalkylene modified polysiloxane shown by the formula I and formula II (R is alkyl, phenyl, or floroalkyl; Y and Z are R and/or X, when b=0, at least one of them is X, and when bnot equal to 0, at least one of them is R; X is group shown by the formula III; A1 and A2 are 2-4C alkylene, A2 is preferably propylene and/or tetramethylene; R' is H, alkyl, or acyl; m is 10-100; a and b are 0 or >=1), having >=7,000 average molecular weight, subjected to a substrate, and subjected to wet treatment.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for manufacturing sheet materials.

[Conventional technology]

Conventionally, as a method for manufacturing a sheet material by applying a polyurethane solution to a substrate and then wet-processing, a sheet material having an oxyethylene group and an oxypropylene group and having an average molecular weight of 600 is described in Japanese Patent Publication No. 58-39451.
There is a method of improving the wet coagulability of polyurethane by incorporating polyoxyalkylene-modified dimethylpolysiloxane of ~6000 into a polyurethane solution.

However, the sheet material obtained by this method has excellent wet film formability and hydrolysis resistance, and has excellent wet film formability and hydrolysis resistance due to the polyoxyalkylene-modified dimethylpolysiloxane remaining in the sheet material. As a result of intensive studies to obtain a sheet material with a good surface appearance, the present invention was achieved.

[Means to solve the problem]

The present invention provides a method for producing sheet materials by applying a solution of polyurethane to a substrate and then wet-processing, in which a polyurethane solution containing a general formula (wherein R is an alkyl group, a phenyl group, a fluoroalkyl group, etc.) Y and Z are R and/or X, and when b=o, at least one represents X, and when b-+00, at least one represents R. X is +A, A20, A, A2 are each an alkylene group having 2 to 4 carbon atoms, R' is a hydrogen atom, an alkyl group, or an acyl group. m is 10 to 100. a, b
The average molecular weight of the polyoxyalkylene-modified polysiloxane compound is 7,000 or more J:! O or 1 like this
This is a method for producing a sheet material characterized by containing a polyoxyalkylene-modified polysiloxane compound represented by the above integer.

In general formulas (1) and (2), examples of the alkyl group for R include alkyl groups having 18 or less carbon atoms, such as methyl, ethyl, hexyl, octyl, decyl, and octadecyl groups. As the fluoroalkyl group, -CH2CH2CF3. -CH2CH2C6F, 3
Examples include ゜. Among R, preferred is a methyl group.

It will be done. Among these, preferably -CH2CH2CH2
− is.

Examples of the alkylene group having 2 to 4 carbon atoms for A2 include ethylene group, propylene group, and tetramethylene group. Among these, preferred are a propylene group and/or a tetramethylene group.

Examples of ÷A20+- include polyoxyalkylene chains mainly composed of oxypropylene groups and/or oxytetramethylene groups. A2o is an oxypropylene group or an oxytetramethylene group.

Combined use of oxypropylene group and oxytetramethylene group,
Examples include a combination of these groups and an oxyethylene group. When used in combination, either random or block combination may be used, but random is preferable. ÷A20+,
The molar ratio of (oxypropylene group and/or oxytetramethylene group) to oxyethylene group is usually 9
It is 0/10 to 10010, preferably 10010.

Examples of the alkyl group for K' include the same alkyl groups as for R. In addition, the acyl group of R' has 1 carbon number.
~20 acyl groups (e.g. acetyl groups).

stearoyl group, etc.).

Among R', preferred are a hydrogen atom, a methyl group, a butyl group, and an acetyl group.

m is preferably 15-70.

In a and b, the average molecular weight of the polysiloxane compound is 700.
It is an integer of 0 or 1 or more, such as 0 or more, preferably 9000 or more. If the average molecular weight is less than 7.000, the polysiloxane compound remaining in the sheet material bleeds out quickly onto the sheet surface, adversely affecting the surface appearance of the sheet material.

Further, a and b are integers of 0 or 1 or more such that the content of X is usually 20 to 80%, preferably 30 to 70% of the average molecular weight of the polysiloxane compound.

The content of X is 20% of the average molecular weight of the polysiloxane compound
If it is less than 80% or more than 80%, wet film forming properties will not be sufficient even if it is contained in a polyurethane solution.

The amount of the polysiloxane compounds represented by formulas (1) and (2) is usually 10% by weight or less, preferably 0.5 to 5% by weight, based on the solid content of the polyurethane solution.

Examples of the polyurethane in the present invention include polyurethane or polyureaurethane having a substantially linear structure composed of an organic diisocyanate, a polymeric diol, and optionally a chain extender.

Examples of organic diisocyanates include aromatic diisocyanates (4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, etc.), araliphatic diisocyanates (xylylene diisocyanate, etc.), aliphatic diisocyanates (hexamethylene diisocyanate, lysine diisocyanate, etc.), and alicyclic diisocyanates. Examples include diisocyanates (isophorone diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, etc.). Details are described in JP-A-53-42294. Practically preferred among these are aromatic diisocyanates, and particularly preferred are aromatic diisocyanates (4.4').
-diphenylmethane diisocyanate (hereinafter abbreviated as MDI).

Examples of the polymeric diol include polyether diol, polyester diol, polyether ester diol, polymer diol, and mixtures of these with a length of 2 m or more. As polyether diol, alkylene oxide [
Polymerization or copolymerization (block or random) of ethylene oxide (hereinafter abbreviated as JJ), propylene oxide (hereinafter abbreviated as PO), butylene oxide, etc.), heterocyclic ether (tetrahydrofuran, etc.), For example, polyethylene ether glycol, polypropylene vinyl glycol, polyethylene-propylene (block or random) ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, polyoctamethylene ether glycol, and two or more thereof. Mixtures may be mentioned.

Examples of polyester diols include dicarboxylic acids (adipine, succinic acid, sebacic acid, and glutaric acid).

maleic acid, fumaric acid, phthalic acid, etc.) and glycols [
Ethylene glycol, propylene glycol, 1,3-
Butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, 1,8-octamethylene diol, neopentyl glycol, bis(hydroxymethyl)cyclohexane.

bis(hydroxyethyl)benzene, alkyl dialkanolamine, etc.), such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene butylene adipate 2 polyethylene propylene adipate;
Examples include polylactone diols such as polycaprolactone diols; and mixtures of two or more thereof.

As polyether ester diols, ether group-containing diols (such as the above-mentioned polyether diols, diethylene glycol, triethylene glycol, dipropylene glycol, etc.) or mixtures of these and other glycols can be used with the above-mentioned dicarboxylic acids or dicarboxylic acid anhydrides (phthalic anhydride, etc.). acid, maleic anhydride, etc.) and alkylene oxide, such as poly(polytetramethylene ether) adipate. As a polymer diol, JP-A-53-167
No. 96, JP-A-58-42294, JP-A-53-79
No. 965 publications, polymer diols (the above-mentioned polyether diols, polyester diols, and/or
or polyether ester diol) or a mixture of these and a medium to low molecular weight diol. The average molecular weight (as measured by hydroxyl value) of the polymeric diol is usually 500 to 5,000, preferably 1,000 to 3,000.

Chain extenders include those described in JP-A-53-42294, such as low molecular weight diols (ethylene glycol, propylene glycol, 1.4-7'tanediol,
1,6-hexanediol, etc.), aliphatic diamines (ethylene diamine, etc.), alicyclic diamines (isophorone diamine, etc.), aromatic diamines (4,4'-diaminodiphenylmethane, etc.), araliphatic diamines (xylene diamine, etc.) , alkanolamines (such as ethanolamine), hydrazine, dihydrazides (such as adipic acid dihydrazide), and mixtures of two or more thereof. Preferred among these are low molecular weight glycols. Particularly preferred are ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and mixtures of two or more thereof. The molar ratio of the polymeric diol and the chain extender used if necessary is:
The ratio is usually 1:0 to 10, preferably 1:2 to 5. The average molecular weight of a diol that is a combination of a high molecular weight diol and a chain extender (when a low molecular weight diol is used as a large chain extender) is usually 300 to 800. If the average molecular weight of the diol is greater than 800, the wet film forming properties of the polyurethane will be poor, and if it is smaller than 300, the wet film forming property of the polyurethane will be good, but a hard polyurethane will be obtained, resulting in poor bending resistance, especially at low temperatures. The bending resistance is not sufficient.

In the production of polyurethane, the ratio of organic diisocyanate to polymeric diol and chain extender used if necessary is usually isocyanate group: active hydrogen-containing group = 0.
．． 9 to 1.1:1 (equivalent ratio), preferably substantially 1. When the ratio is outside the above-mentioned normal range, it is difficult to produce polyurethane with a high degree of polymerization.

The method for producing polyurethane may be any known method.
b) One-shot method, for example, a method in which an organic diisocyanate, a polymeric diol, and, if necessary, a chain extender are simultaneously reacted; (0) Prepolymer method, for example, a method in which a polymeric diol and an organic diisocyanate are reacted to form a terminal N-terminated
An example of this method is to obtain a CO prepolymer and extend the chain using a chain extender.

Among these, the one-shot method is preferred.

The above production can be carried out in the presence or absence of a solvent inert to isocyanate groups. Suitable solvents in the presence of a solvent include amide solvents [dimethylformamide (hereinafter abbreviated as DMF), dimethylacetamide, etc.], sulfoxide solvents (dimethylsulfoxide, etc.), ether solvents (dioxane, tetrahydrofuran, etc.). ), ketone solvents (cyclohexanone, methyl ethyl ketone, etc.), ester solvents (ethyl acetate, etc.), aromatic hydrocarbon solvents (toluene, etc.), and two or more of these solvents.

Practically preferred solvents are amide solvents and sulfoxide solvents, and particularly preferred is DMF.

In the production of polyurethane, the reaction temperature may be the same as that normally employed in the polyurethanization reaction in the industry, and when a solvent is used, the reaction temperature is usually 20 to 100%.
℃, and when no solvent or medium is used, it is usually 20 to 220
°C1 is preferably 150 to 200 °C. To accelerate the reaction, amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.) and tin catalysts (trimethyltin laurate, dibutyltin dilaurate, etc.) used in normal polyurethane reactions are used.
may be used. In addition, if necessary, a polymerization terminator such as a monohydric alcohol (methanol, butanol).

cyclohexanol, etc.), monovalent amines (methylamine, butylamine, cyclohexylamine, etc.), etc. can also be used.

Polyurethane can be produced using production equipment commonly employed in the industry. Moreover, when a solvent is not used in the case, manufacturing equipment such as a kneader or an extruder can be used. The polyurethane produced in this way has a 30% by weight (solid content) solution viscosity measured as a DMF solution of 2.000 to 1,000,000 cps.
/20″C is practically preferable.

As the polyurethane solution used for producing the sheet material, a polyurethane solution produced in the presence of a solvent inert to the isocyanate groups can be used, or a polyurethane solution prepared by dissolving the polyurethane in the solvent can be used. You can also use

The concentration of the solution is usually 5 to 30% by weight, preferably 10 to 3% by weight.
It is 0% by weight.

The polyurethane solution contains resins other than polyurethane resins, such as polyvinyl chloride, polyacrylic ester, polymethacrylic ester, polystyrene, polyacrylonitrile, acrylonitrile-vinylidene chloride copolymer,
A vinyl chloride-vinyl acetate copolymer may also be blended. In addition, if necessary, antioxidants (hintered phenols such as 4,4'-butylidene-bis(3-methyl-6-t-butylphenol); organic phosphites such as triphenyl phosphite and trichloroethyl phosphite), ultraviolet rays, etc. Absorbents (benzophenone, benzotriazole, etc.), stabilizers such as carboxylic acids, phosphoric acids, oxycarboxylic acids, halogenated phenols, pigments (titanium oxide, carbon black, etc.), fillers (calcium carbonate, etc.), plasticizer.

Antistatic agents, bactericidal agents, and known coagulation regulators [higher alcohols (Japanese Patent Publication No. 42-22719), crystalline organic compounds (Japanese Patent Publication No. 56-41652), hydrophobic nonionic surfactants (Japanese Patent Publication No. 45-1972) -89634 and Japanese Patent Publication No. 45-39685)] can also be added.

Examples of the substrate include a nonwoven fabric, a woven fabric, a raised fabric (release paper, etc.), a plastic film, a glass plate, and the like. Alternatively, the substrate may be resin-treated with a polymeric substance in advance, such as a nonwoven fabric.

In the case of fibrous substrates such as knitted fabrics, woven fabrics, raised fabrics, polymeric substances (polyurethanes such as conventional polyurethanes and polyurethanes from organic diisocyanates such as polyether polyols and/or polyester polyols, chain extenders and organic diisocyanates) are used in advance. etc.) can also be used. Resin processing methods include impregnating the substrate with a solution or dispersion of a polymeric substance;
Alternatively, a method of subsequent wet processing may be mentioned.

Methods for applying the polyurethane solution to the substrate include coating and/or impregnating methods.

Next, wet processing is performed. Liquids (nonsolvents) used in wet processing include water, ethylene glycol, glycerin, ethylene glycol monoethyl ether, hydroxyethyl acetate, and mixtures thereof. Furthermore, a mixture of the above-mentioned non-solvent and the above-mentioned solvent (mixing ratio: 90:10-30, usually 90:10 to 30, by weight) can also be used. Preferred among these are mixtures of water and solvents and water.

Wet processing methods include conventional methods such as immersing the substrate to which a polyurethane solution has been applied in a coagulating bath, coagulating with water vapor, partially coagulating with water vapor (≦), and then immersing the substrate in a coagulating bath, and polyurethane solution. There is a method of adding a non-solvent to the substrate and applying it to the substrate as a colloidal dispersion, and immersing it in a coagulation bath.A conventional wet processing method is described in U.S. Pat. No. 8,284,274, columns 10-11 (
It is also described as methods a), (b), (c), and (d).

After wet processing, remove solvent and wash (water) using the usual method.

(e.g., methanol). Anionic, nonionic, cationic or amphoteric surfactants can also be used to promote solvent removal. Also British Patent No. 116887
Crosslinking treatment can also be carried out by the method described in No. 2.

The obtained sheet material may be used as it is or after being peeled off from the substrate (in the case of using a plastic film, release paper, glass plate, etc.).

The sheet material obtained by the method of the present invention consists of a porous polyurethane layer obtained by coating a substrate with a polyurethane solution, wet-processing it, and then peeling off the substrate;
) consisting of a base layer and a porous polyurethane coating layer obtained by coating a base with a polyurethane solution and wet-processing;
(C) A base layer having a porous polyurethane-impregnated layer obtained by impregnating a base with a polyurethane solution and wet-processing; ) After applying a polyurethane solution on it, wet treatment or■)
obtained by laminating thereon a wet-processed polyurethane film made by coating on another substrate.
Examples include those having a resin-treated base layer and a porous polyurethane coating layer. Among these, the preferred one is (
c) and ii).

〔Example〕

The present invention will be further illustrated by the following examples, but the present invention is not limited to these examples.

Examples 1-8 and Comparative Examples 1-2 Polyethylene adipate 400 with a molecular weight of 2000!
(0.2 mol) and 1,4-butanediol 49.4F (
0.55 mol) and 31! 148
After adding 6f of DMF and dissolving it uniformly, MDI 187
J'j (0.75 mol) was added and reacted at 60-70"C. 10 hours after the start of the reaction, the viscosity was 90,000 cps/20
A transparent and uniform polyurethane solution of "C" was obtained. Black toner [Dilac Black (Dilac Black)
) 5 parts of Dainippon Ink Chemical Industry ■Product] and 1.5 parts each of polyoxyalkylene-modified polysiloxane compounds having the compositions described in Examples 1 to 3 and Comparative Examples 1 to 2 of Table 1 were added. 1. with polyester film. □wit
The porous sheet was coated to a thickness of 20°C and immersed in a 20% DMF water bath adjusted to 20°C for 10 minutes to form a coagulated film.Then, this porous sheet was peeled off from the polyester film and further coated at 20°C. After washing by immersing in warm water at 30°C for 90 minutes, the sheet was dried with hot air at 100°C for 20 minutes to obtain a black porous sheet. The appearance and properties of the obtained black porous sheet were as shown in Table 2.

In addition, the black porous sheet obtained above (7cIrLX7
CIrL) was immersed in a 1% NaOH aqueous solution at room temperature for 6 hours, and the liquid content of the aqueous solution contained in the sheet was measured using the following formula. Further, the sheet was placed horizontally at room temperature to dry, and then treated under steaming at 1.10° C. for 28 hours. After the treatment, the sheet was folded and checked for cracks. The test results are shown in Table-2.

(Reference) This test shows that when a porous sheet is used as a shoe material, if the porous sheet itself easily absorbs sweat or salt solution from the outside, deterioration may be accelerated during wear. As this is expected, this test will be adopted as a preliminary test.

Further, a black porous sheet (7cI'fL x 7cIrL) was placed in a 40'c Gafu dryer, and the presence or absence of bleed-out material on the surface was carefully observed, and the number of days in which it occurred was recorded. The test results are shown in Table-2.

The porous sheet obtained by the present invention has excellent surface smoothness,
Moreover, a uniform microporous layer without curling phenomenon was obtained, and the hydrolysis resistance was also good, and there was no generation of bleed-out substances on a calendar day and the surface appearance was good, whereas Comparative Examples 1 to 3
Although the porous sheet No. 2 has a uniform microporous layer, it has poor hydrolysis resistance and bleed-out substances occur due to T4I, resulting in poor surface appearance and is not practical in terms of commercial value. Ta.

〔Effect of the invention〕

The sheet material obtained by the present invention has excellent wet film forming properties and hydrolysis resistance, and has a good surface appearance. It also has excellent air permeability, and is also excellent in feel, flexibility, and physical properties (tensile strength, elongation, abrasion resistance, bending resistance, etc.). Furthermore, the surface is dense and has high strength, and the interior has excellent air permeability and flexibility.

Claims (1)

[Claims] 1. A method for producing sheet materials by applying a solution of polyurethane to a substrate and then wet-processing, wherein the polyurethane solution contains a general formula ▲mathematical formula, chemical formula, table, etc.▼ ( 1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) (In the formula, R is a non-reactive group such as an alkyl group, phenyl group or fluoroalkyl group. Y and Z are R and/or X, When b=0, at least one represents X, and when b≠0, at least one represents R.
(A_1O)-(A_2O)-_mR', A_1, A
Each of _2 is an alkylene group having 2 to 4 carbon atoms, and R' is a hydrogen atom, an alkyl group, or an acyl group. m is 10-10
It is 0. a and b represent an integer of 0 or 1 or more such that the average molecular weight of the polyoxyalkylene-modified polysiloxane compound is 7,000 or more. ) A method for producing a sheet material, characterized by containing a polyoxyalkylene-modified polysiloxane compound represented by: 2. -(A_2O) in general formulas (1) and (2)
2. The manufacturing method according to claim 1, wherein -_m is a polyoxyalkylene chain mainly composed of oxypropylene groups and/or oxytetramethylene groups. 3. -(A_2O)-_m of general formulas (1) and (2)
The molar ratio of (oxypropylene group and/or oxytetramethylene group) to oxyethylene group is 90
The manufacturing method according to claim 1 or 2, wherein the ratio is from /10 to 100/0. 4. According to any one of claims 1 to 3, wherein the content of X in general formulas (1) and (2) is 20 to 80% of the average molecular weight of the polyoxyalkylene-modified polysiloxane compound. Manufacturing method described. 5. The content of the polyoxyalkylene-modified polysiloxane compound is 10% by weight based on the solid content of the polyurethane solution.
The manufacturing method according to any one of claims 1 to 4, wherein the amount is as follows.